Hexahydro-4H-Indeno Acetonide Fragrance Compound

ABSTRACT

A novel compound 4H-indeno[1,2-D]-1,3-dioxole, 3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl 1 is disclosed as well as the use of the compound as a fragrance chemical. The fragrance compound is suitable for use in creating fragrances, and scents in items such as perfumes, colognes and personal care products.

RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.11/008,705, filed Dec. 9, 2004, now allowed.

FIELD OF THE INVENTION

The present invention is directed to a novel compound and the use ofthis novel compound as a fragrance chemical suitable for incorporationin fine fragrances, cosmetics, toiletries and related applications.

BACKGROUND OF THE INVENTION

There is an ongoing need in the fragrance industry to provide newchemicals to give perfumers and others persons ability to create newfragrances for perfumes, colognes and personal care products.

U.S. Pat. No. 4,902,840, hereby incorporated by reference, discusses theuse of substituted tetrahydroindane derivatives as useful fragrancechemicals. U.S. Pat. No. 6,303,798 hereby incorporated by reference,discusses the use of4,4a,5,6,7,8,9,9b-octahydro-7,7,8,9,9-pentamethyl-indano[4,5-d]-dioxinas a fragrance chemical. A commonly owned patent application Ser. No.10/618,363, filed Jul. 10, 2003, hereby incorporated by reference,discusses a compound4,4a,5,6,7,8,9,9b-octahydro-7,7,8,9,9-pentamethyl-indano[4,5-d]-dioxinand its use in perfumery.

Despite this disclosure and numerous other patents on fragrancematerials, there is a continuing need to provide additional fragrancematerials such that perfumers may create new fragrances for variousapplications.

SUMMARY OF THE INVENTION

The present invention provides a novel chemical, and the use of thischemical to enhance the fragrance of perfumes, toilet waters, colognes,personal products and the like. In addition, the present invention isdirected to the use of the novel chemical to enhance fragrance inperfumes, toilet waters, colognes, personal products and the like.

The present invention is directed to the compound3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl-4H-indeno[1,2-D]-1,3-dioxole,use of3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl-4H-indeno[1,2-D]-1,3-dioxoleas a fragrance chemical to enhance fragrance in perfumes, toilet waters,colognes, personal products and the like. More specifically, the presentinvention is directed to the compound having the structure set forthbelow as well as a method for enhancing a perfume by incorporating anolfactory acceptable amount of compounds of the formula:

These and other embodiments of the present invention will be apparent byreading the following specification.

DETAILED DESCRIPTION OF THE INVENTION

The compound3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl-4H-indeno[1,2-D]-1,3-dioxoleis well suited for incorporation in fragrance formulations. Thepreparation of the3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl-4H-indeno[1,2-D]-1,3-dioxoleis set forth in Example 1 below from4,5,6,7-tetrahydro-3,3a,7,7-tetramethyl-3aH-indene. Preparation of4,5,6,7-tetrahydro-3,3a,7,7-tetramethyl-3aH-indene is discussed in U.S.Pat. No. 3,911,027, the contents of which are incorporated herein byreference.

We have discovered that3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl-4H-indeno[1,2-D]-1,3-dioxolehas a strong, woody ambery, odor or note, that is well suited for use asa fragrance chemical.

Those with skill in the art will appreciate that novel compound of thepresent invention has various isomers. As used throughout thisspecification 3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl-4H-indeno [1,2-D]-1,3-dioxole includes variousisomers and isomer blends. The isomers include, but are not limited tothe isomers set forth below:(3aR,3bR,8aS)-3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl-4H-indeno[1,2-D]-1,3-dioxole,

(3aS,3bR,8aR)-3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl-4H-indeno[1,2-D]-1,3-dioxole,

(3aS,3bS,8aR)-3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl-4H-indeno[1,2-D]-1,3-dioxole,

(3aR,3bS,8aS)-3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl-4H-indeno[1,2-D]-1,3-dioxole

These isomers can be prepared by techniques known in the art. Suchtechniques include but are not limited to stereoselectivedihydroxylation. Other techniques for separating the isomers includedistillation and other techniques suitable for separating isomers. Thepresent invention contemplates the use of the stereoisomer mixtures aswell as the preparation and/or isolation of the selective isomers.

The use of this novel compound is widely applicable in current perfumeryproducts, including the preparation of perfumes and colognes, theperfuming of personal care products, such as soaps, bath and showergels, body washes, and hair care products as well as air fresheners,candles and cosmetic products including but not limited to mascara,make-up, eyebrow liner, eyebrow pencil, rouge, cake make-up and thelike. The compound can also be used to perfume candles and cleaningagents, such as, but not limited to soaps, detergents, dishwashingmaterials, scrubbing compositions, window cleaners, and the like.

In these preparations, the compound of the present invention can be usedalone or in combination with other fragrance compositions, solvents,adjuvants and the like. Those with skill in the art will appreciate thenature and variety of the other ingredients that can be used incombination with the compound of the present invention.

Many types of fragrances can be employed in the present invention, theonly limitation being the compatibility with the other components beingemployed. Suitable fragrances include but are not limited to fruits suchas almond, apple, cherry, grape, pear, pineapple, orange, strawberry,raspberry; musk, flower scents such as lavender-like, rose-like,iris-like, and carnation-like. Other pleasant scents include herbal andwoodland scents derived from pine, spruce and other forest smells.Fragrances may also be derived from various oils, such as essentialoils, or from plant materials such as peppermint, spearmint and thelike.

A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891,the contents of which are incorporated by reference as if set forth inits entirety. Another source of suitable fragrances is found inPerfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher,1959. Among the fragrances provided in this treatise are acacia, cassie,chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle,hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cuthay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose,vanilla, violet, wallflower, and the like.

As used herein olfactory effective amount is understood to mean theamount of fragrance ingredient in perfume compositions the individualcomponent will contribute to its particular olfactory characteristics,but the olfactory effect of the perfume composition will be the sum ofthe effects of each of the perfume or fragrance ingredients. Thus theingredients of the invention can be used to alter the aromacharacteristics of the perfume composition by modifying the olfactoryreaction contributed by another ingredient in the composition. Theamount will vary depending on many factors including other ingredients,their relative amounts and the effect that is desired.

The level of compound of the invention employed in the perfumed articlevaries from about 0.005 to about 20 weight percent, preferably fromabout 0.01 to about 10 and most preferably from about 0.5 to about 5weight percent. In addition to the fragrance compound of the presentinvention, other agents can be used in conjunction with the fragrance.Well known materials such as surfactants, emulsifiers, and polymers toencapsulate the fragrance can also be employed without departing fromthe scope of the present invention.

Another method of reporting the level of the fragrance compound of theinvention in the perfumed composition, i.e., the compounds as a weightpercentage of the materials added to impart the desired fragrance. Thecompounds of the invention can range widely from 0.005 to about 10weight percent of the perfumed composition, and preferably from about0.1 to about 5 weight percent. Those with skill in the art will be ableto employ the desired level of the compound of the invention to providethe desired fragrance and intensity.

The following examples are provided as specific embodiments of thepresent invention. Other modifications of this invention will be readilyapparent to those skilled in the art, without departing from the scopeof this invention. As used herein all percentages are weight percentunless noted to the contrary.

EXAMPLE 1 Preparation of 4H-Indeno[1,2-D]-1,3-Dioxole,3A,3B,5,6,7,8A-Hexahydro-2,2,3A,3B,7,7-Hexamethyl

A five liter, four neck flask equipped with a stirrer with stir shaft,thermometer, thermowatch, water condenser, addition funnel and isopropylalcohol/dry ice cooling bath was charged with 3.5 grams of BF₃•Et₂O, 790grams of acetone and 360 grams of 4,5,6,7-tetrahydro-3,3a,7,7-tetramethyl-3 aH-indene. Preparation of 4,5,6,7-tetrahydro-3,3a,7,7-tetramethyl-3aH-indene is discussed in U.S. Pat. No. 3,911,027.Peracetic acid (37%), 535 grams, was fed to the reaction flask over aperiod of two hours at ambient temperature. The resulting reaction wasexothermic and the cooling bath was used to control the reactiontemperature to 25-30° C. After the diene addition was concluded thereaction was allowed to age for an additional 3 hours. Water (500 mL)and 750 mL of 10% aqueous Na₂SO₃ were added to quench the reaction andthe layers were separated. The organic phase was washed with saturatedNa₂CO₃ solution. The crude product was distilled to provide 234 grams(boiling point 100-104° C. at 2 mmHg) of the acetonide, which is about a45% theoretical yield.

¹H NMR (360 MHz, CDCl₃) 5.39 ppm (s, 1H), 4.57 ppm (s, 1H), 1.86-1.75ppm (m, 1H), 1.60-1.48 ppm (m, 2H), 1.42 ppm (s, 3H), 1.41 ppm (s, 3H),1.29 ppm (s, 3H), 1.23 ppm (s, 3H), 1.14 ppm (s, 3H), 1.11 ppm (s, 3H),0.94-1.18 ppm (m, 3H).

EXAMPLE 2 Fragance Composition Containing the Compound of the PresentInvention

DPG is understood to mean dipropylene glycol. Unless noted to thecontrary all of the following fragrance materials are available fromInternational Flavors & Fragrances Inc., New York, N.Y. Material PartsARMOISE ESSENCE 5.0 AMBRETTOLIDE 1% in DPG 30 Citronellol 40Alpha-damascone 10% DEP (Firmenich) 1 Dimethyl benzyl carbinyl butyrate2 DPG 88 4-Ethyloctanal 20 FLOROL (Firmenich) 6 FRUCTONE 11 Galbascone1% (DPG) 60 Ginger Oil 1.0 Iso cyclo Citral 1% DPG 1.0 KOAVONE (IFF) 36LIFFAROME “PFG” 10% in DPG 40 Litsea cubeba oil 15 MAGNOLAN (Haarman &Reimer) 9 Magnolia flower oil 10% in DEP 4.0 MAGNOLAN 9.0 Phenylacetaldehyde (50%) 2.5 Phenyl ethyl alcohol 130 Rose oxide 10% in DPG 13Triplal Extra 5.5 VELOUTONE 10% in DPG (Firmenich) 25 TOTAL 550.0

The compound of the present invention was admixed in DPG to form a 10%solution. Ninety parts of the second solution was admixed with the abovefragrance formulation. The resulting formulation was described as havinga green, mossy note, partially through the incorporation of3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl-4H-indeno[1,2-D]-1,3-dioxole.

The above fragrance formulation was presented to demonstrate theeffectiveness of the compound of the present invention in enhancing,improving or modifying the performance of the formulations in which itis incorporated.

1. A process for making3a,3b,5,6,7,8a-hexahydro-2,2,3a,3b,7,7-hexamethyl-4H-indeno[1,2-D]-1,3-dioxolecomprising reacting of4,5,6,7-tetrahydro-3,3a,7,7-tetramethyl-3aH-indene, acetone andperacetic acid.
 2. The process of claim 1 conducted in the presence ofBF₃•Et₂O.